Patent GB-473762-A (GB)
Title: Improvements in the manufacture and production of derivatives of 1.4-diaminoanthraquinone
IPC: C09B1/26
Filed: 1936-04-17
Abstract: Dyes are made by reacting sulphuric esters of primary hydroxyalkylamines with 1.4-diaminoanthraquinones in presence of reducing agents or with leuco compounds of 1.4-diaminoanthraquinones. Anthraquinones specified are 1.4-diamino-, 1.4.5-triamino-, 1.4.5.8-tetramino-and 1.4-diamino-5.8-dihydroxyanthraquinone and also 1-amino-4-alkyl, -aryl, aralkyl or cycloalkyl-aminoanthraquinones or 1.4-dialkylaminoanthraquinones in which the alkyl groups may be different.  Sulphuric esters specified are those of ethanolamine, the propanolamines, the butanolamines, the aminohexyl alcohols or hydroxyalkylamines of higher molecular weight.  The reaction is effected by heating the components in a diluent, and a mixture of the 1.4-diaminoanthraquinone with its leuco compound may be used. Reducing agents specified are alkali hyposulphites or zinc dust, and diluents specified are water, aliphatic alcohols, ethers and ketones or mixtures of water and aliphatic alcohols.  In addition to the sulphuric ester, the 1.4-diaminoanthraquinone may be reacted simultaneously with a sulphuric ester of another primary hydroxyalkylamine or with any primary amine.  When this primary amine is an arylamine or a heterocyclic amine, it is preferably used in the form of its salt with a mineral acid, or the reaction is carried out in presence of a mineral acid, e.g. hydrogen chloride, or in presence of boric acid.  Acid salts such as sodium or ammonium bisulphite may be used as condensing agents.  Mild oxidizing agents may be used such as a slow current of air, sodium perborate, or a 1.4-dihydroxyanthraquinone, to effect oxidation of the leuco compounds simultaneously with the condensation, or the oxidation may be carried out subsequently, preferably in presence of copper or a copper compound and/or a secondary or tertiary amine such as piperidine or dimethylaniline.  A 1.4-dihydroxyanthraquinone may also be added to the reaction mixture in some cases.  Some of the products are blue dyes for acetate artificial silk (see Specification 285,641, [Class 2 (iii)]), or for wool.  In examples: (1) leuco-1.4-diaminoanthraquinone is condensed with the sodium salt of ethanolamine sulphuric ester in aqueous methanol; copper acetate and piperidine are then added and air is led through the reaction mixture giving the sodium salt of the sulphuric ester of 1.4-dimonohydroxyethylaminoanthraquinone; the ethanolamine sulphuric ester salt may be replaced by the corresponding ester salts of 1.2 or 1.3 propanolamine or of 1.2 - butanolamine or mixtures thereof; (2) leuco - 1.4 - diaminoanthraquinone is reacted with ethanolamine sulphuric ester and methylamine in aqueous methanol in presence of caustic soda; the mixture is then oxidized as in (1) to give the sodium salt of the sulphuric ester of 1-methylamino-4-hydroxyethylaminoanthraquinone; the methylamine may be replaced by ethylamine, n-propylamine, n-butylamine, n-amylamine, hexylamine, heptylamine, ethanolamine, 1.2- or 1.3-propanolamine and the ethanolamine sulphuric ester may be replaced by the ester of 1.2- or 1.3-propanolamine or of 1.2-butanolamine; (3) leuco-1.4-diaminoanthraquinone is reacted with ethanolamine sulphuric ester and benzylamine as in (2) to give the sodium salt of the sulphuric ester of 1-benzylamino-4-hydroxyethylaminoanthraquinone; the benzylamine may be replaced by b -phenylethylamine, cyclohexylamine, or 2-amino-1.2.3.4-tetrahydronaphthalene and the ethanolamine sulphuric ester may be replaced by the esters of 1.2- or 1.3-propanolamine; (4) leuco-1.4-diaminoanthraquinone is reacted with the sodium salt of 1.2-propanolamine sulphuric ester in aqueous methanol in presence of 1.4-dihydroxyanthraquinone; (5) p 1.4.5.8-tetraminoanthraquinone is heated with ammonia in aqueous methanol in presence of sodium hyposulphite to 60--70 DEG  C. for half an hour, and then reacted with ethanolamine sulphuric ester and caustic soda, followed by oxidation with a stream of air; the tetraminoanthraquinone may be replaced by 1.4-diamino-5.8-dihydroxyanthraquinone and the ethanolamine sulphuric ester may be replaced by 1.2- or 1.3-propanolamine or 1.2-butanolamine sulphuric esters or mixtures thereof, or mixtures of the said esters with amines; (6) 1-amino-4-hexahydroanilinoanthraquinone is treated as in (5), the oxidation being performed in presence of copper acetate and piperidine, to give the sodium salt of the sulphuric ester of 1-hydroxyethylamino-4-hexahydroanilinoanthraquinone; the 1-amino-4-hexahydroanilinoanthraquinone may be replaced by 1 - amino - 4 - methylaminoanthraquinone, 1-amino-4-hydroxyethylaminoanthraquinone, 1 - amino - 4 - n - butylaminoanthraquinone, 1-amino-4-anilinoanthraquinone, 1-amino-4-p-toluidoanthraquinone, 1-amino-4-p-aminoanilinoanthraquinone or 1-amino-4-p-hydroxyanilinoanthraquinone; (7) leuco-1.4-dimethylaminoanthraquinone is reacted with the sodium salt of ethanolamine sulphuric ester as in (1) to give the same product as (1); the leuco-1.4-dimethylaminoanthraquinone may be replaced by the 1.4-diethyl- or 1-methyl-4-ethyl body.